Process for breaking petroleum emulsions



,. ters or weak brines.

iatented Feb. 20, 1951 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, St. Louis, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application May 5, 1950, Serial No. 160,379

19 Claims.

This invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions. This invention is a continuation in part of our copending application Serial No. 64,466, filed December 10, 1948, in turn a continuation in part of application Serial No. 726,218, filed February 3, 1947 (both now abandoned). See also our copending application, Serial No. 8,731, filed February 16, 1948 (now abandoned), and also Serial No. 42,134, filed August 2, 1948 (now abandoned). Attention is directed also to our copending application Serial No. 64,469, filed December 10, 1948.

Complementary to the above aspect of the invention is our companion invention concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of such chemical compounds, prodriots, and the like, in various other arts and industries, along with the method for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. See our copending application Serial No. 64,467, filed December 10, 1948.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft wa- Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

Demulsification as contemplated in the present application includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the ab- 2 sence of such precautionary measure. similarly, such demulsifier may be mixed with thehydrocarbon component.

Briefly stated, the present process is concerned with the breaking or resolving of petroleum emulsions by means of certain esters which are, in turn, derivatives of specific synthetic products. These products are, in turn, the oxyalkylated derivatives of certain resins hereinafter specified.

Thus, the present process is concerned with the breaking of petroleum emulsions of the waterin-oil type characterized by subjecting the emulsion to the action of a mixed hydrophile ester in which the acyl radicals are those of a detergent-forming monocarboxy acid having at least 8 and not over 32 carbon atoms in conjunction with the acyl radical of a polycarboxy acid, and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methyl-glycide, and (B) an oXyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenolaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R. is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the 2,4,6 position said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R10)n, in which hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus; there being present, in the ester, at least one acyl radical of the polycarboxy acid and at least one acyl radical of the detergent-forming monocarboxy acid, statistically taken, per resin molecule; and with the final proviso that the hydrophile properties of said ester, as well as said oxyalkylated resin, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorouslywith one to three volumes of water.

For purpose of convenience what is said hereinafter will be divided into four parts. Part 1 will be concerned with the production of the resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; Part 3 will be concerned with the conversionof the immediately aforementioned derivative into a total or partial ester by reaction with an acid, an ester, or other functional derivative, so as to obtain a compound of the kind previously specified and PART 1 As to the preparation of the phenol-aldehyde presins reference is made to our copending applications, Serial Nos. 8,730 and 8,731, both filed 'February 16, 1948 (both now abandoned).

In such copending applications we described a fusible, organic solvent-soluble, water-insoluble resin polymer of the formula In such idealized representation n" is a numeral varying from 1 to 13 or even more, provided that r the resin is fusible and organic solvent-soluble. ,R is a hydrocarbon radical having at least 4 and .not over 8 carbon atoms. .cation R may have as many as 12 carbon atoms, asin the case of a resin obtained from a dodecylphenol. first suitable to describe the alkylene oxides employed as reactants, then the aldehydes, and

In the instant appli- In the instant invention it may be finally the phenols, for the reason thatthe latter require a more elaborate description. 7

The alkylene oxides which may be used are the alpha-beta oxides having not more than 4 carbon atoms, to wit, ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene oxide, glycide, and methylglycide.

Any aldehyde capable of forming a methylol or a substituted methylol group and having not Y more than8 carbon atoms is satisfactory, so long as itdoes not possess some other functional 1 group or structure which will conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of an aqueous solution, for the production of the resins is particularly advantageous. Solid polymers of form- 4 aldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive. Furthermore, the higher aldehydes may undergo other reactions which are not desirable, 5 thus introducing difficulties into the resinification step. Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self-resinification when treated with strong acids or alkalies. On the other hand, higher aldehydes frequently beneficially affect the solubility and fusibility of a resin. This is illustrated, for example, by the difierent characteristics of the resin prepared from para-tertiary amylphenol and formaldehyde on one hand, and a comparable product prepared from the same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle, solid, whereas the latter is soft and tacky, and obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particu-- larly benzaldehyde. The employment of furfural requires careful control for the reason that in addition to its aldehydic function, furfural can form vinyl condensations byvirtueof its unsaturated structure. The production of resins from furfural; for use in preparingreactants for the present process is most conveniently conducted with weak alkaline catalysts and often with' .alkali metal carbonates. ,Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, Z-ethylhexanal, r ethylebutyraldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use of glyoxal should be avoided due to the fact that it is tetrafunctional. However, our experience has been that,- in resin manufacture and-particularly as described herein, apparently only one of the aldehydic functions enters into the resinification reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Needless to say, one can use a mixture of two or more aldehydes although usually this has no advantage.

Resins of the kind which are used as intermediates'in this invention are obtained with the use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts they enter into the condensation'reaction and, in fact, may operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine .illustrates'such a combination. In light of these variousreactions it becomes diflicult to present any for-mulawhich would depict the structureof the various resins prior to oxyalkylation. -M-ore will -be said subsequently as to the difference between *the useof analkaline catalyst and an acid catalystj even' in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where different basic materials are employed. The basic materials employed include not only those previously enumerated but 20' also the hydroxides of'the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids such as sodium acetate, etc.

Suitable phenolic reactants include the following: Para-tertiarybutylphenol; para-secondarybutylphenol; para tertiary amylphenol; parasecondary amylphcnol; para-tertiary-hexylphen01; para-isooctylphenol; ortho phenylphenol; para-phenylphenol; orthobenzylphenol; parabenzylphenol; and para-cyclohexylphenol, and the corresponding ortho-para substituted metacresols and 3,5-xylenols. Similarly, one may use para-, or ortho-nonylphenol or a mixture, paraor ortho-decylphenol or a mixture, menthylphenol, or paraor ortho-dodecylphenol.

For convenience, the phenol has previously been referred to as monocyclic in order to differentiate from fused nucleus polycyclic phenols, such as substituted naphthols. Specifically, "monocyclic is limited to the nucleus in which the hydroxyl radical is attached. Broadly speaking, where a substituentis cyclic, particularly aryl, obviously in the usual sense such phenol is actually polycyclic although the phenolic hydroxyl is not attached to a fused polycyclic nucleus. Stated another way, phenols in which the hydroxylgroup is directly attached to a condensed or fused polycyclic structure, are excluded. This matter, however, is clarified by the following consideration. The phenols herein contemplated for reaction may be indicated by the followin formula:

in which R is selected from the class consisting of hydrogen atoms and hydrocarbon radicals having at least 4 carbon atoms and not more than 12 carbon atoms, with the proviso that one occurrence of R is the hydrocarbon substituent and the other two occurrences are hydrogen atoms,

. and with the further provision that one or both j of the 3 and positions may be methyl substituted.

' The above formula possibly can be restated more conveniently in the following manner, to wit, that the phenol employed is of the following formula, with the proviso that R is a hydrocarbon substituent located in the 2,4,6 position, again with the provision as to 3 or 3,5 methyl substitution. This is conventional nomenclature, numboring the various positions in the usual clockwise manner, beginning with the hydroxyl position as one:

particularly by one having at least 4 carbon atoms and not more than 12 carbon atoms, is well known. As has been previously pointed out, there is no objection to a methyl radical provided it is present in the 3 or 5 position.

iii)

Thermoplastic or fusible phenol-aldehyde res ins are usually manufactured for the varnish trade and oil solubility is of prime importance. For this reason, the common reactants employed are butylated phenols, amylated phenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenol-formaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difficulty, while when a water-insoluble phenol is employed some modification is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large interfacial area. Once the reaction starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion of an organic sulfo-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydrochloric acid. For example, alkylated aromatic sulfonic acids are effectively employed. Since commercial forms of such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such alkali salt plus a small quantity of strong mineral acid, as shown in the examples below. If desired, such organic sulfoacids may be prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the phenol. In such cases where xylene is used as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfo-acid. Addition of a solvent such as xylene is advantageous as hereinafter described in detail. Another variation of procedure is to employ such organic sulfo-acids, in the form of their salts, in connection with an alkali-catalyzed resinification procedure. Detailed examples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin by the acid catalytic procedure is that, since a difunctional phenol is employed, an excess of an aldehyde, for instance formaldehyde, may be employed without too marked a change in conditions of reaction and ultimate product. There is usually little, if any, advantage, however, in using an excess over and above the stoichiometric proportions for the reason that such excess may be lost and wasted. For all practical purposes the molar ratio of formaldehyde to phenol may be limited to 0.9 to 1.2, with 1.05 as the preferred ratio, or sufficient, at least theoretically, to convert the remaining reactive hydrogen atom of each terminal phenolic nucleus. Sometimes when higher aldehydes are used an excess of aldehydic reactant can be distilled off and thus recovered from the reaction mass. This same procedure may be used with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased over the simple stoichiometric ratio of one-to-one or thereabouts. With the use of alkaline catalyst it has been recognized that considerably increased amounts of formaldehyde may be used, as much as two moles of formaldehyde, for example, per mole of phenol, or even more,

cyclic polymers instead of linear polymers;

alysts to produce low-stage resins.

age 7 to units. 1"low-stage resin or low-stage intermediate is employed to mean a stage having 6 or 7 units or with the result that only a small part of suc aldehyde remains- 'uncombinedor is subsequently liberated during resinification. Structures which have been advanced to explain such increased use of aldehydes are the following:

Such structures may lead to the production of For this reason, it has been previously pointed out that, although linear polymers have by far the most important significance, the present invention does not exclude resins of such cyclic structures.

into resins of higher molecular weight, by heating along with the employment of vacuum so as to split off water or formaldehyde, or both. Generally speaking, temperatures employed, particularly with vacuum, ma be in the neighborhood of 175 to 250 C., or thereabouts.

It may be well to point out, however, that the amount of formaldehyde used may and does usually aiTect the length of the resin chain. Increasing the amount of the aldehyde, such as formal 'dehyde, usually increases the size or molecular weight of 'the polymer.

In the hereto appended claims there is specified, among other things, the resin polymer containing at least 3 phenolic nuclei. Such minimum molecular size is most conveniently determined as a rule by cryoscopic method using benzene, or

' some other suitable solvent, for instance, one of those mentioned elsewhere herein as'a solvent for *such' resins.

As a matter of fact, using the procedures herein described or any conventional ""resinification procedure will yield products usually having definitely in excess of 3 nuclei.

In other words, a resin having an average of 4, 5 or 5 /2 nuclei per unit is apt to be formedas a minimum in resinification, except under certain special conditions where dimerization may occur; 1

However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, etc.', or some other'suitable solvent which boils or refluxes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked excess of formaldehyde or other aldehyde, then the average size of the resin is apt to be distinctly over the above values, for example, it may aver: Sometimes the expression employing acid catalysts.

" tion of both types of catalysts is used in different stages of resinification. Resins so also perfectly satisfactory.

even less. In the appended claims we have used -low-stage to-mean3to7 units based on average molecular weight. F In the esters used in accord ance with the invention, those derived from low stage resins, as just defined, will contain at least one acyl radical of a polycarboxy acid and one acyl radical of a detergent-forming monocarboxy acid for each '7 phenolic nuclei. In higher stage resins, the ratio may be smaller. However, itis advantageous, even withhigher stage resins, to introduce at least one acyl radical of each type of acidfor every 7 phenolic nuclei.- This does not mean, of course, that each resin molecule has one acyl radical of each type linked to it, as the radi- The molecular weight determinations, of course, require that the product be completely soluble' in the particular solvent selected as, for instance, benzene. The molecular weightdetermination of such solution may involve either the freezing point as in the cryoscopic method, or, less con veniently perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is. that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method for determining the molecular weights of resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co. 1947)v Subsequent examples will illustrate the use of an'acid catalyst; an alkaline catalyst, and no catalyst. As far as resin manufacture per se is concerned, we prefer to use an acid catalyst,-and particularly a mixture of an organic sulfo-acid and a mineral acid, along with a suitable solvent,

such as xylene, as hereinafter illustrated in de- 'tail. However, we have obtained products from resins obtained by use "of an alkaline catalyst which were just as satisfactory as those obtained Sometimes a combinaobtained are 'In numerous instances the higher molecular weight resins, i. e., those referred to as high-stage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost certain to produce further polymerization. For instance. acid catalyzed resins obtained in the usual manner and having a molecular weight indicating the presence of approximately 4 phenolic units or thereabouts may be subjected to such treatment, with the result that one obtains a resin having approximately double this molecular weight. The usual procedure is to use a secondary step, heating the resin in the presence or absence of an inert gas, including steam,,or by use of vacuum.

'2 moles of a phenol and one mole of formaldehyde,

particularly where the substituent has 4 ;or 5

carbon atoms. Where the number of carbon atoms in a substituent approximates the upper limit specified herein, there may be some tendeney to dimerization. Ihe usual procedure to obtain a dimer involves an enormously large excess of the phenol, for instance, 8 to 10 moles per mole of aldehyde. Substituted dihydroxydiphenylmethanes obtained from substituted phenols are not resins as that term is used here- Although any conventional procedure ordinarily employed may be used in the manufacture of the herein contemplated resins or, for that matter, such resins may be purchased in the open market, we have found it particularly desirable to use the procedures described elsewhere herein, and employing a combination of an organic sulfo-acid and a mineral acid as a cata yst, and xylene as a solvent. 'By way of illustration, certain subse u nt examples are included, but it is to be understood the herein described invention is not concerned with the resins per se or with any particular method of manufacture but is concerned with the use of reactants obtained by the subsequent oxyalkylation thereof. The phenol-aldehyde resins may be prepared in any suitable manner.

Oxyalkylation, particularly oxyethylation which is the preferred reaction, depends on contact between a non-gaseous phase and a gaseous hase. It can, for example, be carried out by melting the thermoplastic resin and subjecting it to treatment with ethylene oxide or the like, or by treatihg a suitable solution or suspension. Since the melting points of the resins are often higher than desired in the initial stage of oxyethylation, we have found it advantageous to use a solution or su pension of thermoplastic ije's'in in an inert solvent such as xylene. Under such circumstances, the resin obtained in the usual manner is dissolved by heating in xylene uiider a reflux condenser or in an other suitable mamier. Since xylene or an equivalent inert solvent is present or may be present during oxyalkylation, it is obvious there is no objection to having a solvent present during the resinifying stage if, in addition to being inert towards the resin, it

' is also inert towards the reactants and also inert towards water. n merous solvents, particularly hf aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, c'ymene, ethyl benzene, propyl benzene, inesitylene, decalin (decahydronaphthalene), tetralin (tetrahydronaphthalene), ethylene glycol diethylether, diethylene glycol diethylether, and tetraethylene glycol dimethylether, or mixtures of one or more. Solvents such as dichloroethylether, or dichloroprcpylether may be employed either alone or in mixture but have the objection that the chlorine atom in the compound may slowly combine with the alkaline catalyst employed in oxyethylation. Suitable solvents may be selected from this group for molecular weight determinations.

The use of such solvents is a convenient expedient in the manufacture of the thermoplastic resins, particularly since the solvent gives a more liquid reaction mass and thus prevents overheating, and also because the solvent can be employed in connection with a reflux condenser and a water trap to assist in the removal of water of reaction and also water present as part of the formaldehyde reactant when an aqueous solution of formaldehyde is used. Such aqueous solution, of course, with the Ordinary product of com- 10 merce containing about 3'7 /2% to 40% formaldehyde, is the preferred reactant. When such solvent is used it is advantageously added at the beginning of the resinification procedure or before the reaction has proceeded very far.

The solvent can be removed afterwards by distillation with or without the use of vacuum, and a final higher temperature can be employed to complete reaction if desired. In many instances it is most desirable to permit part of the solvent, particularly when it is inexpensive, e. g., xylene, to remain behind in a predetermined amount so as to have a. resin which can be handled more conveniently in the oxyalkylation stage. If a more expensive solvent, such as decalin, is employed, xylene or other inexpensive solvent may be added after the removal of decalin, if desired.

In preparing resins from difunctional phenols it is common to employ reactants of technical grade. The substituted phenols herein contemplated are usually derived from hydroxybenzene. As a rule, such substituted phenols are comparatively free from unsubstituted phenol. We have generally found that the amount present is considerably less than 1% and not infrequently in the neighborhood of 6 of 1%, or even less. The amount of the usual trifunctional phenol, such as hydroxybenzene or metacresol, which can be tolerated is determined by the fact that actual cross-linking, if it takes place even infrequently, must not be suflicient to cause insolubility at the completion of the resinification stage or the lack of hydrophile properties at the completion of the oxyalkylation stage.

The exclusion or such trifunctional phenols as hydroxybenzene or inetacresol is not based on the fact that the mere random or occasional in clusion of an unsubstituted phenyl nucleus in the resin molecule oi in one of several molecules, for example, markedly alters the characteristics of the ox'yalkylated derivative. The presence of a phenyl radical having a reactive hydrogen atom available or having a hydroxymetliylol or a sub-' stituted hydroxymethylol group present is a potential source of cross-linking either during resinification or oxyalkylation. Cross-linking leads either to insolub1e resins or to non-hydrophilic products resulting from the oxyalkylation procedure. With this rationale understood, it is obvious that trifunctiona1 phenols are tolerable only in a minor proportion and should not be present to the extent that insolubility is produced in the resins, or that the product resulting from oxyalkylation is gelatinous, rubbery, or at least not hydrophile. As to the rationale of resinification, note particularly what is said hereafter in differentiating between resoles, Novolaks, and resins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organic solvent-soluble resins are usually linear but may be cyclic. Such more complicated structure may be formed, particularly if a resin prepared in the usual manner is converted into a higher stage resin by heat treatm nt in vacuum as previously mentioned. This again is a reason for avoiding any opportunity for cross-linking due to the presence of any appreciable amount of trifunctional phenol. In other words, the presence of such reactant may cause cross-linking in a conventional resinification procedure, or in the oxyalkylation procedure or in the heat and vacuum treatment if it is employed as part of resin manufacture.

Our routine procedure in examining a phenol forsuitability forpreparing intermediates used in practicing the invention is to prepare; a resin employing formaldehyde in excess (1.2 moles of formaldehyde per mole of phenol) and usinganacid catalyst in the manner described in, Example 1a of our Patent 2,499,370, granted March 7, 1950. If the resin so. obtained is solventsolublein any one of the aromatic or other solvents previouslyreferred to, it is then subjected to oxyethylation. During oxyethylation a temperatureis employed of approximately 150 to 16,5;with ddition of at least 2 and advantageously up to 5 moles of ethylene oxide per phenolic hydroxyl. The oxyethylation isadvantageouslyconducted so as to require from a few minutes up to 5tto hours. If the product so obtained is solvent-soluble and self-dispersingor emulsifiable, or has emulsifying properties, the phenol is perfectlysatisfactory from the standpoint of trifuctional phenol content. Thesol: vent may beremoved prior to the dispersibility or emulsifiability test. When a product becomes rubbery during oxyalkylation due to the presence of a small, amount of trireactive phenol, as previouslymentioned, orfor some other reason, it may, become extremely insoluble, and no longer qualifies as being hydrophile as herein specified. Increasingv the size of the aldehydic nucleus, for instance using heptaldhyde instead of formaldehyde, increases tolerance for trifunctional phenol.@ :aThe presence-of a trifunctional or tetrafunc tional phenol (such asresorcinolor bisphenol A) is apt to produce detectable cross-linking and insolubilization but will not necessarily do so, especiallyif theproportion is small. Rsinification involving difunctional phenols only may also produce insolubilization, although this seemsto bean anomaly or a contradiction of what is sometimes said inregard to resinification reactions involving difunctional phenols only. This is presumably due to cross-linking. This appears to becontradictory to what one might expect in light ofthe theory of functionality in resihification. .It is true that under ordinary circumstances, or rathr under the circumstances of conventional resin manufacture, theprocedures employingdifunctional phenols are very apt to, and almost invariably do, yield solvent-soluble, fusible resins. However, when conventional procedures are employed in connectionwith resins for. varnish manufacture or the like, thlr'e is involved the matter of color, solubility in oil, etc, Whenresins of the same type are manufactured for-the herein contemplated purpose, 1. e., asa raw material to be subject d to oxyalkylation, such criteria of selection are no longer pertinent. Stated another way, one may use more drastic conditions of resinificaticn than those ordinarily employed to produce resins for the pr sent purposes. Such more drastic conditions of resinifica tion may include increasqd amounts of catalyst, higher temperatures, longer time of reaction, subsequent reaction involving heat alone or in combinationwith vacuum, etc. Therefore, one is not only concerned with the resinification reactions which yield the bulk of ordinary resins, from difunctional phenols but also and particularly with the minor reactions of ordinary resin manufacture which are of importance in the present inventionfor the reason that they occur under more drastic conditions of resinification which may be employed advantageously at times, and they may lead to cross-linking. v

In this connection it may be well to point out that part of these reactions are now understood orexplainable to a greater or lesser degree in light of a most recent investigation. Reference is made to the researches of Zinke and his coworkers, Hultzsch and his associates, and to Von Eulen and his co-workers, and others. As toa bibliography of such investigations, see Carswell, Phenoplasts, chapter 2. These investigators limited much of their work to reactions involving phenols having two or less reactive hydrogen atoms. 'Much of what appearsin these most recent and most up-to-date investigations is pertinent to the present invention insofar that much of it is referring to resinification involving difunctional phenols.

For. the moment, itrnay be simpler to consider a most typical type of fusible resin and forget for the time that such resin, at least under certain circumstances, is susceptible to further compli cations. Subsequently in the text it will be pointed out that cross-linking or reaction with excess formaldehyde may take place even with one of such most typical type resins. This point is made for the reson that insolubles must be avoided in order to obtain the products herein contemplated for use as reactants.

The typical type. of fusible resin obtained from a para-blocked or ortho-blocked phenol is clearly. differentiated from the Novolak type or resole type of resin. Unlike the resole type, such typical type part-blocked ,or otho-blocked phenol resin may be heated indefinitely without. passing into an infusibl stage, and in this re-v spectissimilar to a Novolak. Unlike the Novalak type the addition of a further reactant for in,- stance, more aldehyde, does not ordinarily alter asibility of the difunctional phenol-aldehyde type resin; but such additionto a Novolak causes cross-linking ,by virtue of the available third functional position.

What has been said immediately preceding is subject tomcdification in this respect: It is well known, for example, that difunctional phenols, for instance, paratertiaryamylphenol, and an aldehyde, particularly formaldehyde, may yield heat-hardenable resins, at least under certain conditions, as for example the use of two moles of formaldehyde to one of phenol, along with an alkaline catalyst. This peculiar hardening or curing .or cross-linking of resins obtained from difunctional phenols has been recognized by various authorities.

, The intermediates herein used must be hydrophile or sub-surface-active or surface-active as hereinafter described, and this precludes the formation of insolubles during resin manufacture or the subsequent stage of resin manufacture where heat alone, or heat and vacuum, are em ployed, or in the oxyalkylation procedure. In its simplest presentation the rationale of resinifica tion involving formaldehyde, for example, and a difunctional phenol would not be. expected to form cross-links. However, cross-linking sometimes occurs and it may reach the objectionable stage. However, provided that the preparation of resins simply takes into cognizance the present knowledge of the subject, and employing preliminary, exploratory routine examinations as herein indicated, there is not the slightest difficulty in preparing a very large number of resins of various types and from various reactants, and by means of different catalysts by different procedures, all of which are eminently suitable for the herein described purpose.

Now returning to the thought that cross-linking can take place, even when difunctional phenols are used exclusively, attention is directed to-the following: Somewhere during the course of resin manufacture there may be a potential cross-linking combination formed but actual cross-linking may not take place until the subsequent stage is reached, i. e., heat and vacuum stage, or oxyalkylation stage. This situation may be related or exp ained in terms of a theory of flaws, or Lockerstellen, which is employed in explaining flaw-forming groups due to the fact that a CHzOH radical and H atom may not lie in the same plane in the manufacture of ordinary phenol-aldehyde resins.

Secondly,- the formation or absence of formation of insolubes may be related to the aldehyde used and the ratio of aldehyde particularly formaldehyde. insofar that a slight variation may, under circumstances not understandable, produce insolubiliration, The formation of the insoluble resin is apparently very sensitive to the quantity of forma dehyde employed and a slight increase in the proportion of formaldehyde may lead to the formation of insoluble gel lumps. The cause of insoluble resin formation is not clear. and nothing is known as to the structure of these resins.

All that has been said previously herein as regards resinification has avoided the specific reference to activity of a meth ene hydrogen atom. Actually there is a possibility that under some drastic conditions cross-linking may take place through formaldehyde addition to the methylene bridge. or some other reaction involving a methylene hydrogen atom.

Finally, there is some evidence that, although the meta positions are not ordinarily r'active, possibly at times methylol groups or the like are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal crosslinking.

Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant. In other words, a phenol-aldehyde resin which is thermo-plastic and solventesoluble, particularly if Xylene-soluble, is perfectly satisfactory even though retreatment with more aldehyde may change its characteristics markedly in regard to both fusibility and solubility. Stated another way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or not formaldehyderesistant.

Referring again to the resins herein contemplated as reactants, it is to be noted that they are thermoplastic phenol-aldehyde resins derived from difunctional phenols and are clearly distinguished from Novolaks or resoies. When these resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparatively fluid at 110 to 165 C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

Reference has been made to the use of the word fusible. Ordinarily athermoplastic resin is identified as one which-can be heat d repeatedly and still not lose its thermopiasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heating may become insoluble in an organic solvent, or at, least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the present invention is concerned, it is obvious that a resin to be suitable need only be sufficiently fusible to permit processing to produce our oxyalkylated products and not yield insolubles or cause insolubilization or gel formation, or rubberiness, as previously described. Thus resins which are, strictly speak ing, fusible but not necessarily thermoplastic in the most rigid sense that such terminology would be applied to the mechanical prop. rties of a resin, are useful intermediates. The bulk of all fusible resins of the kind herein described are thermoplastic. 7 ,7 V ,7 V

The fusible or thermoplastic resins, or solventsoluble resins, herein employed as reactants, are water-insoluble, or have no appreciable hydrophile properties. troduced by oxyalkylation. In the hereto appended claims and elsewhere the expression water-insoluble is used to point out this characteristic of the resins used.

In the manufacture of compounds herein employed, particularly for demulsification, it is obvious that the resins can be obtaimd by one of a number of procedures. In the first place, suitable resins are marketed by a number of companies and can be purchased in the open market; in the second place, there are a wealth of examples of suitable resins described in the literature. The third procedure is to follow the directions of the present application.

Th polyhydric reactants, i. e., the oxyalkylahon-susceptible, water-insoluble, organic solvent- .soluble, fusible, phenol-aldehyde resins derived from difunctional phenols, used as intermediates to produce the products used in accordance with the invention, are exemplified by Examples Nos. la through 103a of our Patent 2,499,370, granted March 7, 1950, and reference is made to that pat nt for examples of the oxyalkylated resins used as intermediates.

Previous reference has been made to the use of a single phenol as herein specified, or a single reactive aldehyde, or a single oxyalkylating agent. Obviously, mixtures of reactants may be employed, as for example a mixture of parabutylphenol and para-amylphenol, or a mixture of para-butylphrnol and para-hexylphenol, or para-butylphenol and para-phenylphenol It is extremely difiicult to depict the structure of a resin derived from a single phenol. When mixtures of phenols are used, even in equimolar proportions, the structure of the resin is even more indeterminable. In other words, a mixture involving para-butylphenol and para-amylphenol might have an alternation of the two nuclei or one might have a series of butylated nuclei and then a series of amylated nuclei. If a mixture of aldehydes is employed, for instance, acetaldehyde and butyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure of the resin becomes even more complicated and possibly depends on the relative reactivity of the aldehydes. For that matter, one might be producing simultaneously two different resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyallrylate with ethylene oxide and then finish off with propylene oxide. It is understood that the oxyalkylated The hydrophile property is in- 17v ene oxide which can be eliminated by volatilization or distillation in any suitable manner.

Attention is directed to the fact that the resins herein described must be fusible or soluble in an organic solvent. Fusible resins invariably are soluble in one or more organic solvents such as those mentioned elsewhere herein. It is to be emphasized, however, that the organic solvent employed to, indicate or assure that the resin meets this requirement need not be the one used in oxyalkylation. Indeed, solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and alcohol-ethers. However, where a resin is soluble in an organic solvent, there are usually available other organic solvents which are not susceptible to oxyalkylation, useful for the oxyalkylation step. In any event, the organic solvent-soluble resin can be finely powdered, for instance to 100 to 2'00 mesh, and a slurry or suspension prepared in xylene or the like, and subjected to oxyalkylation. The fact that the resin is soluble in an organic solvent or the fact that it is fusible means that it consists of separate molecules. Phenol-aldehyde resins of the type herein specified possess reactive hydroxyl groups and are oxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned with ability to vary the hydrophile properties of the hydroxylated intermediate reactants from minimum hydrophile properties to maximum hydrophile properties. Such properties in turn, of course, are affected subsequently by the acids employed for esterification and the quantitative nature of the esterification itself, i. e., whether it is total or partial. It may be well, however, to point out what has been said elsewhere in regard to the hydroxylated intermediate reactants. See, for examp e, our co-pending applications, Serial Nos. 8,730 and 8,731, both filed February 16, 1948, and Serial No. 42,133, filed August 2, 1948, and Serial No. 42,134, filed August 2, 1948 (all four cases now abandoned). The reason is that the esterification, depending on the acids selected, may vary the hydrophilehydrophobe balance in one direction or the other, and also invariably causes the development of some property which makes it inherently different from the reactants from which the derivative ester is obtained.

Referring to the hydrophile hydroxylated intermediates, even more remarkable and equally difficult to explain, are the versatility and the utility of these compounds considered as chemical reactants as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the point where two ethyleneoxy radicals or moderately in excess thereof are introduced per phenolic hydroxyl. such minimum hydrophile property or sub-surface-activity or minimum surface-activity means that the product shows at least emulsifying properties or self-dispersion in cold or even in warm distilled water to 40 C.) in concentrations of 0.5% to 5.0%. These materials are generally more soluble in cold water than warm water, and may even be very insoluble in boiling water. Moderately high temperatures aid in reducing the viscosity of the solute under examination. Sometimes if one continues to shake a hot solution, even though cloudy or containing an insoluble phase, onefinds that solution takes place to give a homogeneous 'phaseas the mixture 18 cools. Such self-dispersion tests are conducted in the absence of an insoluble solvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2 moles of ethylene oxide per phenolic nucleous or the equivalent) but insufficient to give a 501 as described immediately preceding, then, and in that event hydrophile properties are indicated by the fact that one can produce an emulsion by having present 10% to 50% of an inert solvent such as xylene. All that one need to do is to have a xylene solution within the range of 50 to parts by weight of oxyalkylated derivatives and 50 to 10 parts by weight of xylene and mix such solution with one, two or three times its volume of distilled water and shake vigorously so as to obtain an emulsionwhich may be of the oil-inwater type or the water-in-oil type (usually the former) but, in any event, is due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility is not suflicient to permit the simple sol test in water previously noted.

If the product is not readily Water soluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethylene glycol diefihylether, with a little acetone added if required, making a rather concentrated solution, for instance 40% to 50%, and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 0.5% to 5.0% strength solution. If the product is self-dispersing (i. e., if the oxyalkylated product is a liquid or a liquid solution self-emulsifiable) such sol or dispersion is referred to as at least semi-stable in the sense that sols, emulsions, or dispersions prepared are relatively stable, if they remain at least for some period of time, for instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 C.) Needless to say, a test can be made in presence of an insoluble solvent such as 5% to 15% of xylene, as noted in previous examples. If such mixture, 1. e., containing a water-insoluble solvent, is at least semi-stable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements hereinaiter described. One outstanding characteristic property indicating surface-activity in a material is the ability to form a permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in the lower and intermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the final product in relation to the hydrophile properties of the final product. The principle involved in the manufacture of the herein contemplated compounds for use as polyhydric reactants is based on the conversion of a hydrophobe or non-hydrophile compound or mixture of compounds into products which are distinctly hydrophile, at least to the extent that they have emulsifying properties or are self-emulsifying; that is, when shaken with water they produce stable or semi-stable suspensions, or, in the presence of a water-insoluble solvent, such as xylene, an emulsion. In demulsification, it is sometimes preferable to use a product having markedly enhanced hydrophile properties over 19 and above the initial stage 'of-self-emulsifiability, although we have found that with products of the "typeused herein, most efiicacious results are obtainedwvith products which do not have hydro- ,phile properties beyond-the stage of self dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. *Such conventional surface-activity may be measured by determining the-surface tension and the interfacial tension against paraffin oil or the like. At theinitial and lower stages of oxyalkylation, "surface-activityis not suitably determined in this sarne manner but one may employ an emulsification test. Emulsions come into existence as a rule through the presence of a surface-active emulsifying agent. Some surface-active emulsifying agents such -'as mahogany soap may produce a water-in-oil emulsionor an oil-in-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying'agent, etc.

The same is true in regard to the oxyalkylated "resins herein specified, particularly in the lower stage of o-xyalkylation, the so-called sub-surrate-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oX-yalkylated resin is dissolved in an equal weight of xylene. Such 53-50 solution is then mixed with 1-3 volumes of water and shaken to produce anemulsion. The amount of xylene is invariably suflicient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions soproduced are usually xylene-in-water emulsions .(oil-in- :water type) particularly when the amount ofdis- -till'ed water usedis at least slightlyin excess of Lthelvolumeof xylene solution and also if shaken avigorously. times, particularly in the lowest stage of .oxyalkylation, one may obtain a waterin=xylene emulsion (water-in-oil type) which is aptzto reverse on-m'ore vigorous shaking and fur- :t'her dilution with water.

Ifindoubt as to thisproperty, comparison with ia iresin obtained from para-tertiary butylphenol and formaldehyde .(ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followedbyoxyalkylation using v2 moles of ethyl- .i'eneioxide for eachiphenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the-above :em'ulsification test.

Ina few instances, the resin may not be .sufli- -ciently soluble in xylene alone but may require the addition of some ethylene glycol diethylether .as described elsewhere. It is understood that such mixture, .or any other similar mixture, is .considered thee quivalent of xylene-for the purpose of this'test.

In many :cases, there is no doublt as to thepres- :BllCe or absence .of hydrophile or surface-active characteristics in the polyhydric reactants used ini'accordance with'this invention. They dissolve or disperse in water; and .such dispersions foam readily. 'With 'borderlineocases, i. e., those which show only incipient hydrophile or surfaceactive property (subsurface-activity) tests for emulsifying properties or selfdispersibility are useful. The fact thata reagent is capableof producing adispersion in wateris proof that it is distinctly 'hydrophile. In doubtful cases, comparison can 7 20 be made "with the ibutylphenol formaldehyde resin analog wherein 2=molesofethy1eneoxide have beenintroduced for each phenolic nucleus.

*lhe presence of -xylene'or anequivalent water- 'insolubl'e solvent may mask-the point at whicha solvent-free product on mere dilution ina test tube'exhibits self-emulsification. For this reason, if it is desirable'to determine the approximate point where se'lf-emulsification 'begins, then'it is be'tterto eliminate the xylene or equivalent from a small portionof the reaction mixture and test such portion. In some cases-such xylenefree resultant "may show initial or incipient :hydrophile properties, whereas in presence of xylene such properties would not :benoted. In :other cases, -='thefirst objective indication of hydrophile properties may be the capacity of :the material to emuls'ify an 'insoluble solvent suoh as xylene. It is to be emphasized that ihydrophile properties hereinreferredito are such asthose exhibited by incipient "seli -emulsification or the presence of emulsifying properties and :go through the'range of homogenous dispersibility .or admixture with -Water-even in presenc'e of added water-insoluble solvent and minor proportionsof common electrolytes as A occur in oil I field :brines.

Elsewhere; it is pointed foutlthat an emulsification test may be used to determine ranges of surfaceeactivity and that such emulsification tests employ a xylene solution. iStated another Way, Kit is really -immaterial whether a xylene solution produces .a sol or whether .it "merely pro -duces an: emulsion.

In lig'ht"o'f what has "been: said previously in .regard .to the "variation .of range :of 'hydrophile properties, and:al'soin .lightof what has been said as to thevariat'ion :in the effectiveness of -variousaalkyleneoxides, and most particularly of 'allethylene oxide, Itoi'introduce 'hydrophile char- -a-cter, it becomes obvious that there is a wide variation in 'thefamountrof alkylene oxide employedasilongias itl'is'atileast .2 molesper phenolicznuc'leus, for. producing productsusefulfor the practice :ofthisrinvention. Another variation is the molecular size :of the resin chain resulting from ireaction loeti/veen 'Jthe :difunctional phenol and'the aldehyde 'such :as:formaldehyde. It is .well knownthat the size and nature or structure of the 'gresinpolymer obtained varies somewhat with the conditions :of reaction, the proportions of reactants, the nature of the catalyst, etc.

Based on .:molecular ivle'ight determinations, .most "of :the resins "prepared :as .Lherein described, ':particu1arlyiin rthe absence of raisecondary heatling :step, :containiSflIo 6 "or 37 phenolic nuclei with approximately .4 1 :or 15 snuclei :as :an average. -More drastic =:conditions of iresinification yield resins of "greater :chain ..length. Such :more intensiveresinificationiis:aiconventional procedure .:and may .beaemployed if .desired. Molecular .weight, of course, is :measuredi'by any suitable procedure, particularly "by :cryoscopic methods; but :using ':the same :reactants :and using more drastic conditions of 'resinification one usually finds that .highertmolecular' 'WeightsLare indicated by :highenmelting .points of the 'resins and a tendency'to decreased solubility. 'Seewha't'has ibeen. saidelsewhereiherein .regardto a secondary zstepiinvolvingithe:heating of aresin with or -without the. use ofwvacuum.

We Thavre previously :pointedout "that either -=an ralkaline for acid catalyst is :advantageously used1in preparing the resin. .A combination of -.:catalysts is sometimes used .in :two stages; :for instance, an alkaline catalyst is sometimes emresins prepared by ourselves.

21 'ployed in a first stage, followed by neutralization and addition of a small amount of acid catalyst in a second stage. It is generally believed that even in the presence of an alkaline catalyst, the number of moles of aldehyde, such as formaldehyde, must be greater than the moles of phenol employed in order to introduce methylol groups in the intermediate stage. There is no indication that such groups appear in the final resin if prepared by the use of an acid catalyst. It is possible that such groups may appear in the finished resins prepared solely with an alkaline catalyst; but we have never been able to confirm this fact in an examination of a large number of Our preference, however, is, to use anacid-catalyzed resin, particularly employing a forinaldehyde-to-phe'nol' ratio of 0.95 to 1.20 and, as far as we have been able to determine, such resins are free from methylol groups. As a matter of fact, it is probable that in acid-catalyzed resinifications, the methylol structure may appear only momentarily at the very beginning of the reaction and in all probability is converted at once into a more complex structure during the intermediate stage.

One procedure which can be employed in the use of a new resin to prepare polyhydric reactants for use in the preparation of compounds employed in the present invention, is to determine the hydroxyl value by the Verley-Bolsing method or its equivalent. The resin as such, or in the form of a solution as described, is then treated with ethylene oxide in presence of 0.5% to 2% of sodium methylate as a catalyst in stepwise fashion. The conditions of reaction, as far as time or per cent are concerned, are within the range previously indicated. With suitable agitation the ethylene oxide, if added in molecular proportion, combines within a comparatively short time, for instance, a few minutes to 2 to 6 hours, but in some instances requires as much as 8 to 24 hours. A useful temperature range is from 125 to 225 C. The completion of the reaction of each addition of ethylene oxide in stepwise fashion is usually indicated by the reduction. or elimination of pressure. An amount conveniently used for each addition is generally equivalent to a mole or two moles of ethylene oxide per hydroxyl radical. When the amount of ethylene oxide added is equivalent to approximately 50% by weight of the original resin, a sample is tested for incipient hydrophile properties by simply shaking up in water as is, or after the elimination of the solvent if a solvent is present. The amount of ethylene oxide used to obtain a useful demulsifying agent as a rule varies from 70% by weight of the original resin to as much as five or six times the weight of the original resin. In the case of a resin derived from para-tertiary butylphenol, as little as 50% by weight of ethylene oxide may give suitable solubility. With propylene oxide, even a greater molecular proportion is required and sometimes a resultant of only limited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more effective in solubilizing properties than the comparable compounds in which no hydroxyl is present.

Attention is directed to the fact that in the subsequent examples reference is made to the step-wise addition of the alkylene oxide, such as ethylene oxide. It is understood, of course, there is no objection to the continuous addition of alkylene oxide until the desired stage of reaction 22 is reached. in fact, there may be less of a hazard involved and it is often advantageous to add the alkylene oxide slowly in a continuous stream and in such amount as to avoid exceeding the higher pressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft or pitch-like resin at ordinary temperaturesv Such resins become comparatively fluid at to C. as a rule, and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation, and particularly oxyethylation. What has been said previously is submitted primarily to emphasize the fact that these remarkable oxyalkylated resins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these polyhydric alcohols in a surface-active or subsurface-active range without examining them by reaction with a number of the typical acids herein described and subsequently examining the resultant for utility, either in demulsification or in some other art or industry as referred to elsewhere, or as a reactant for the manufacture of more complicated derivatives. A few simple laboratory tests which can be conducted in a routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2- to 1; 6 to 1; 10 to 1; and 15 to 1. From a sample of each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in distilled water, as previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the solvent-free product, then one should test its capacity to form an emulsion when admixed with xylene or other insoluble solvent. If neither test shows the required minimum hydrophile property, repetition using 2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to 1 or 10 to 1 ratio. Such moderate hydrophile character is indicated by the fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol when viewed in a comparatively thin layer, for instance the depth of a test tube. 'Ultimate hydrophile character is usually shown at the 15 to 1 ratio test in that adding a small amount of an insoluble solvent, for instance 5% of xylene, yields a product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is an excellent test for surface activity. Previous reference has been made to the fact that other oxyalkylating agents may-require the use of increased amounts of alkylene oxide. However, if one does not even .ene-or substituted methylene radical.

esam (care :to go to the trouble-f icalculati'ng molecular weights, .one icanrsimply :arbitrarily prepare com.- pounds containing ethylene iOXidG equivalent to about 5.0% :to 175% :by weight, .for example by weight, .of the resin :to be .oxyethy-lated; :asecond example using approximately 200% to 3.001% by weight, and a thirdxexample using abou-t:500% :to 750% byzweight, to explore therangeof hydro.- .phile-hydrophobe .balance.

A practical examination :of .the factor 301' ,ox-yr- .alkylation level .can be made by a .very simple test-usingfa pilot plant autoclave :having'a-capam ity .of about 10 to '15 gallons as hereinafter described. :Such.laboratory-prepared routine 1 compounds can then be tested for solubility and, generally speaking, this is all :thatiis required to give a suitable variety covering :the hydrophilehydrophobe range. All .these itests, ;as stated, areintelded toibe routine'testssandinothing more. They are intended to teach .a person,:evenxthough unskilled in oxyethylation or-oxyalkylation, how -toprepare in a perfectly arbitrary -manner, .a series .of compounds illustrating the hydrophilehydrophobe range.

If one purchases .a thermoplastic or fusible resin on the .open market selectedfrom a suitable number which are available, one might have to makezcertain determinations in order to make the quickest approach .to the appropriate oxyalkylation range. For instance, ;one should know (a) the molecular :size, indicating n e number .of phenolic units; .tb) the nature of the :ald'ehydic-residue, which'is usually EH2; .and: (c;)

(-11: 1 tc- 13. or even more) .is given approximately by the 'forlnula: Kmol.

weight of phenol -2) plusincl. weight ofmetr The molecular weight of the resin would be n times the value for the internal limit plus the values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring internal unit ex ,cept that it has oneextra hydrogen. The right hand terminal unit lacks the methylene bridge element. Using one internal unit ofa resin as ,rthebasic element. a resins molecular weight'is .givenapproximately by'taking (11. plus 2 tirnes the weight of the internal element. Wherethe resin molecule has onlyB phenolic nuclei as in the structure shown, this calculation will be jan approximate weight, oneneed only introduce,

for example, two molal weights of ethylene-oxide or as'lightl-y more, per phenolic mucleus, {to produce a product of minimal .hydrophile. character. Fur- .ther .ox'ya'lkylation gives enhanced hydrophile character. Although we have .preparedand tested ,a large number of oxyethylated products of the type described herein, we {have found no instance .where :the use of less than .2 moles of ethylene oxide per phenolic .nucleus gave desirable products.

Examples l b through 181), and the tables which appear in columns 51 through ,56 of our said Patent 2,499,370 illustrate:oxyalkylation products from resinswhich are useful as intermediates for producing :the esterified products used ,in accordance with the present application, such examples givingiexactand complete details for carrying out the voxyalkylation procedure.

The resins, prior to oxyalkylation, vary from tacky, viscous liquids to hard, high-melting solids. Their color varies from a light yellow through amber, ,to .a ,deep red or even almost black. In the manufacture of resins, particularly hard resins, as the :reaction progresses the reaction -mass frequently goes through a liquid state to *a sub-resinous or semi-resinous state, often characterized by :being tacky .or sticky, to a final complete resin. As the resin is subjected to aoxyalkylationthese same physical changes tend .to take ,place -i-nrev.erse. If one starts with a solid resin, oxyalkyration tends to make it tack :or semi resinous and-,furgther ,oxyalkylation .ma'kes'the tackiness disappear ,and changes the product to a liquid. :Thus, astheresin is .oxyalkylated zit ,clecreases in viscosity, that is, the.-

I comes ,morezliquid ,orchanges :from ,a solid to a liquid, particularly when :it is.-co nverted to the water-dispersible ,or water-soluble stage. The color of the oxyalkylated :derivative is usually 'considerablylighter than the original product from which it :is made, varying from apale straw color tozan -amber or reddish amber. The viscoszity .usually varies from that .of an :oil, like castor oil, to that of a thick viscoussirup. Some products are waxy. The presence of .a solvent, :such as 15% xylene ---or "the :like, .thins the viscosity considerably and also reduces :the colornin dilution. 'N'o undue significance .need .be attached sto thescolor .forthereason that if the same compoundis prepared in glassand-iin iron, the latter usually-has somewhat "darker color. If the resins are prepared as --cust'omar i-ly employed in varnish resin manufacture, i. e., a procedure that excludes the presence of oxygen :during the resin'i- 'fioati'on and subsequent-coolingpf the resin, then of course the initial -resin is much lighter in color. "We'have employedsome 'resinswhich initially are almost water-white and a'ls0 yield a lighter col-- cred final product.

Act ually, in considering *theratio of 'alkylene oxide to addyand we havepreviously pointed out that this can be pro-determinedusing laboratory tests,jit;is our aotualpreference from a practical standpoint .tomake :tests on a small pilot plant scale. Our reason .forso doing is that womake one;run,a nd only one, and [that we have acompleteyseries which shows the proer i e-eil luff introducin t e .oxyalk latin a nt o i stance, the ethyleneoxy radicals. -Our;preferred rpr'ocedure'iis as follows: ewetpreparearsuiha :re'sin, orifor that matterppurchase it inithe, open market. =We employ 8 pounds .of resin andw'4 irpounds' of-xylene and place the resin and xylene in asuita-ble autoclave with an openrefiux-condenser. weprefe-rto heat and stir until the-solu- 25 tion is complete. We have pointed out that soft resins which are fluid or semi-fluid can be readily prepared in various ways, such as the use of ortho-tertiary amylphenol, ortho-hydroxydiphenyl, ortho-decylphenol, or by the use of higher molecular weight aldehydes than formaldehyde. If such resins are used, a solvent need not be added but may be added as a matter of convenience or for comparison, if desired. We then add a catalyst, for instance, 2% of caustic soda, in the form of a 20% to 30% solution, and remove the water of solution or formation. We then shut ofi the reflux condenser and use the equipment as an autoclave only, and oxyethylate until a total of 60 pounds of ethylene oxide have been added, equivalent to 750% of the original resin. We prefer a temperature of about 150 to 175 C. We also take samples at intermediate points as indicated in the following table:

Pounds of Ethylene Percentages Oxide A ded per S-pcund Batch Oxyethylation to 750% can usually be completed within 30 hours and frequently more quickly.

The samples taken are rather small, for instance, 2 to 4 ounces, so that no correction need be made in regard to the residual reaction mass. Each sample is divided in two. One-half the sample is placed in an evaporating dish on the steam bath overnight so as to eliminate the xylene. Then 1.5% solutions are prepared from both series of samples, i. e., the series with xylene present and the series with xylene removed.

Mere visual examination of any samples in solution may be sufficient to indicate hydrophile character or surface activity, 1. e., the product is soluble, forming a colloidal sol, or the aqueous solution foams or shows emulsifying property. All these properties are related through adsorption at the interface, for example, a gas-liquid interface or a liquid-liquid interface. If desired, surface activity can be measured in any one of the usual ways using a DuNouy tensiometer or dropping pipette, or any other procedure for measuring interfacial tension. Such tests are conventional and require no further description. Any compound having sub-surface-activity, and all derived from the same resin and oxyalkylated to a greater extent, i. e., those having a greater proportion of alkylene oxide, are useful as polyhydric reactants for the practice of this invention.

Another reason why we prefer to use a pilot plant test of the kind above described is that we can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydroxybenzene or metacresol satisfactorily. Previous reference has been made to the fact that one can conduct a laboratory scale test which will indicate whether or not a resin, although soluble in solvent, will yield an insoluble rubbery product, i. e.,

a product which is neither hydrophile nor surface-active, upon oxyethylation, particularly extensive oxyethylation. It is also obvious that one may have a solvent-soluble resin derived from a mixture of phenols having present 1% or 2% of a trifunctional phenol which will result in an insoluble rubber at the ultimate stages of oxyethylation but not in the earlier stages. In other words, with resins from some such phenols, addition of 2 or 3 moles of the oxyalkylating agent per phenolic nucleus, particularly ethylene oxide, gives a surface-active reactant which is perfectly satisfactory, while more extensive oxyethylation yields an insoluble rubber, that is, an unsuitable reactant. It is obvious that this present procedure of evaluating trifunctional phenol tolerance is more suitable than the previous procedure.

It may be well to call attention to one result which may be noted in a long draw-out oxyalkylation, particularly oxyethylation, which would not appear in a normally conducted reaction. Reference has been made to cross-linking and its effect on solubility and also the fact that, if carried far enough, it causes incipient stringiness, then pronounced stringiness, usually followed by a semi-rubbery or rubbery stage. Incipient stringiness, or even pronounced stringiness, or even the tendency toward a rubbery stage, is not objectionable so long as the final product is still hydrophile and at least sub-surface-active. Such material frequently is best mixed with a polar solvent, such as alcohol or the like, and preferably an alcoholic solution is used. The point which we want to make here, however, is this:

Stringiness or rubberization at this stage may possibly be the result of etherification. Obviously if a difunctional phenol and an aldehyde produce a non-cross-linked resin molecule and if such molecule is oxyalkylated so as to introduce a plurality of hydroxyl groups in each molecule, then and in that event if subsequent etherification takes place, one is going to obtain crosslinging in the same general way that one would obtain cross-linking in other resinification reactions. Ordinarily there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However, suppose that a certain weight of resin is treated with an equal weight of, or twice its weight of, ethylene oxide. This may done in a comparatively short time, for instance, at or C. in 4 to 8 hours, or even less. On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction required 4 or 5 times as long to introduce an equal amount of ethylene oxide employing the same temperature, then etherification might cause stringiness or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it may be well to repeat the experiment and reach the intermediate stage of oxyalkylation as rapidly as possible and then pro ceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etherification if it be caused by the extended time period.

It ma be well to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethylation, of the thermo- 27 been oxyalkylated, for "instance, .oxyethyla'ted, until it gives a perfectly clear solution, even in the presence of some accompanyingwater-insoluble solvent such as 10% to 15% .of xylene. Further oxyalkylation, particularly ioxyet-hylation, may then yield a product which, instead of giving a clear solution as previously, gives a very milky solution suggesting that some marked change has taken place. One explanation of the above change is that the structural "unit "indicated in the following way where 811 is a fairly large number, for instance, to 20, decomposes and an oxyalkylated resin representing a lower degree of oxyethylation and a less soluble one,

- is generated and a cyclic polymer of ethylene oxide is produced, indicated thus:

This fact, of course, presents no difficulty vfor the reason that oxyalkylation can be conducted in each instance stepwise, or at a gradual irate,

, and samples taken at short intervals so .as to V arrive at a. point where optimum surface activity or hydrophile character is obtained if desired; for products for use as polyhydric reactants in the practice of this invention, this is not necessary and, in fact, may be undesirable, i. e., reduce the .efiiciency of theproduot.

We do not know to what extent oxyalkylation produces uniform distribution in regard to phenolic hydroxyls'present in the resin molecule. In some instances, of course; such distribution can not be uniform for the reason that we have not specified that the molecules of ethylene oxide, for

example, be added in multiples of the units present in the resin molecule. trated in the follow manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum of. two moles of ethylene oxide per phenolic nucleus are added, this would mean an addition of '10 'moles of ethylene oxide, but suppose that one added .11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously, even assuming the most uniform distribution possible, some of the polyethyleneoxy radicals would contain 3 ethyleneoxy units and some would contain 2. Therefore, it is impossible to specify uniform distribution in regard to the entrance of the ethylene oxide or other oxyalkylating agent. For that matter, if one were "to introduce '25 moles of ethylene oxide there is no way to be certain that all chains of ethyleneoxy units would, have 5 units; there might be some having, for example,

j 4 and 6 units, or for that matter 3 or '7 .units. Nor is there any basis for assuming that thenumber of molecules of the oxyalkylatingagent added to each or" the molecules of the resin is the same,

or dilierent. Thus, where formulae are given to illustrate or depict the oxyalkylated products, distributions of radicals indicated are to "be statistically taken.

the total amount of ethylene oxide, or total amount of any other oxyalky'lating agent, to add.

In regard to solubility of the resins and the oxyalkylated compounds, and for that matter derivatives of the latter, the following should be This may be illusnoted. In oxyalkylation, any solvent employed should be non-reactive to the alkylene oxide employed. 7 This limitation does not apply to selvents used "in cryo scopio determinations for obvious reasons. 'Attention is directed to the fact that various organic :solvents may be employed to verify that the resin is organic solvent-soluble. Such solubility test merely characterizes the resin. The particular solvent used in such test may not be suitable for a molecular weight determination and',"likewise, the solvent used in determining molecular weight may not be suitable as a solvent during oxyalkylatio-n. For solution of the oxyalkylated compounds, or their derivatives a great variety of solvents maybe employed, such as alcohols, ether alcohols, 'cresols, phenols, ke-

tones, esters, etc., alone or with the addition of water. Some of; these are mentioned hereafter. We prefer the use; of benzene :or diphenylamine as a solvent in making cryoscopic measurements. The most satisfactory resins are those which are soluble in xylene or the like, rather than those which are soluble-only in some other solvent containing elements other than carbon and hydrogen, for instance, oxygen or chlorine. Such solvents are usually polar, semi-polar, or slightly polar in nature compared with xylene, cymene,

etc.

, determination used, whether cryoscopicmeasure- "ment or otherwise, other than the conventional cryoscopic one employing benzene, should be checked so as to insure that it gives consistent values on such conventional resins as 'a control. Frequently all that is necessary -to make an approximation of the molecular weight range is to make a comparison with the dimer obtained by'chemical combination of two moles of the r same phenol, and one mole of the same aldehyde We have, however, included specific directions and specifications in regard to vices.

under conditions to insure dimerization. As to the preparation of such dimers from substituted phenols, see Carswell, Phenoplasts, page 31. The increased, viscosity, resinous character, and decreased solubility, etc., of the higherjpo'lymers in comparison with the dimer, frequently .are

all that is required to, establish that the resin contains 8 or more structural units per mole- 'cule.

Ordinarily, the ,oxyalkylation is carried out in autoclaves provided with agitators .or stirring de- We have found that the speed of the agitation markedly influences the reaction time. "In

some cases, the change from slow speed agitation, for example, in a laboratory autoclave agitation with a stirrer operating at a speed of 60 to 200 R. P. M., to high speed agitation, with the stirrer operating at 250 to 350 R. P. M. reduces the time required for oxyalkylation by about one-half to two-thirds. Frequently xylene-soluble products which give insoluble products by procedures employing comparatively slow speed agitation, give suitable hydrophile prod uctswhen produced by similar procedure but with high speed agitation, as a result, we believe, of the reduction in the time required with consequent elimination or curtailment of opportunity for curing or etherization. Even if the formation of an insoluble product is not involved, it is frequently advantageous to speed up the reaction, thereby reducing production time, by increasing agitating speed. In large scale operations, we have demonstrated that economical manufacturing results from continuous oxyalkylation, that is, an operation in which the alkylene oxide is continuously fed to the reaction vessel with high speed agitation, i. e., an agitator operating at 250 to 350 R. P. M. Continuous oxyalkylation, other conditions being the same, is more rapid than batch oxyalkylation, but the latter is ordinarily more convenient for laboratory operation.

Previous reference has been made to the fact that in preparing esters or compounds of the kind herein described, particularly adapted for demulsification of water-in-oil emulsions, and for that matter for other purposes, one should make a complete exploration of the wide variation in hydrophobe-hydrophile balance as previously referred to. It has been stated, furthermore, that this hydrophobe-hydrophile balance of the oxyalkylated resins is imparted, as far as the range of variation goes, to a greater or lesser extent to the herein described derivatives. This means that one employing the present invention should take the choice of the most suitable derivative selected-from a number of representative compounds, thus, not only should a variety of resins be prepared exhibiting a variety of oxyalkylations, particularly oxyethylations, but also a variety of derivatives. This can be done conveniently in light of what has been said previously, from a practical standpoint, using pilot plant equipment, for instance, an autoclave having a capacity of approximately three to five gallons. We have made a single run by appropriate selections in which the molal ratio of resin equivalent to ethylene oxide is one to one, 1 to 5, 1 to 10, 1 to 15, and l to 20. Furthermore, in making these particular runs we have used continuous addition of ethylene oxide. In the continuous addition of ethylene oxide we have employed either a cylinder of ethylene oxide without added nitrogen, provided that the pressure of the ethylene oxide was sufficiently great to pass into the autoclave, or else we have used an arrangement which, in essence, was the equivalent of an ethylene oxide cylinder with a means for injecting nitrogen so as to force out the ethylene oxide in the manner of an ordinary seltzer bottle, combined with the means for either weighing the cylinder or measuring the ethylene oxide used volumetrically; Such procedure and. arrangement for injecting liquids is, of course, conventional. The following data sheets exemplify such operations, i. e., the combination of both continuous agitation and taking samples so as to give five different variants in oxy: ethylation. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop immediately if there is any indication that reaction is stopped or, obviously, if reaction is not started at the beginning of the reaction period. Since the addition of ethylene oxide is invariably an exothermic reaction, whether or not reaction has taken place can be judged in the usual manner by observing (a) temperature rise or drop, if any, (17) amount of cooling Water or other means required to dissipate heat of reaction; thus, if there is a temperature drop without the use of cooling water or equivalent, or if there is no rise in temperature without using cooling water control, careful investigation should be made.

In the tables immediately following, we are showing the maximum temperature which is usually the operating temperature. In other words, by experience we have found that if the initial reactants are raised to the indicated temperature and then if ethylene oxide is added slowly, this temperature is maintained by cooling water until the oxyethylation is complete. We have also indicated the maximum pressure that we obtained or the pressure range. Likewise, we have indicated the time required to inject the ethylene oxide as well as a brief note as to the solubility of the product at the end of the oxyethylation period. As one period ends it will be noted we have removed part of the oxyethylated mass to give us derivatives, as therein described; the rest has been subjected to further treatment. All this is apparent by examin ng the col mns headed Starting mix, Mix at end of reaction, Mix which is removed for sample, and Mix which remains as next starter.

The resins employed are prepared in the manner described in Examples Nos. 1a through 10311 of our said Patent 2,499,370 except that instead of being prepared on a laboratory scale they were prepared in 10 to 15-ga lon electro-vapor heated synthetic resin ilot plant reactors, as manufactured by the Blaw-Knox Company, Pittsburgh, Pa., and completely described in their bulletin No. 2087, issued in 1947, with specific reference to Spec. No. 71-3965.

For convenience, the following tables give the numbers of the examples of our said Patent 2,499,- 370 in which the preparation of identical res ns on laboratory scale are described. It is understood that in the following examples, the change is one with respect to the size of the operation.

The solvent used in each instance was xylene. This solvent is particularly satisfactory for the reason that it can be removed readily by distillation or vacuum distillation. In these continuous experiments the speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subseouent tables it will be noted that if a comparatively small sample is taken at each stage, for instance, /2 to one gallon, one can proceed through the entire molal stage of 1 to 1. to 1 to 20, without remaking at any intermediate stage. This is illustrated by Example 104?). In other examples we found it des rable to take a larger sample, for instance, a 3-gallon sample, at an intermediate stage. As a result it was necessary in such instances to start with a new resin sample in order to prepare sufiicient oxyethylated derivatives illustrating the latter stages. Under such circumstances, of course, the earlier stages which had been previously prepared were by-passed or ignored. This is illustrated in the tables where, obviously, it shows that the starting mix was not removed from a previous sample.

Phenol for resin. Parasoety'lphenol Aldehyde for resin: Formaldehyde Date, June 23, 14, 1948 [Resinmade in pilot plant sizebatch. approximately 25 pounds. corresponding to 8a of Patent 2,499,370 but this batch designated 114a.]

- 4 Mix Which is Mix Which Re- Starting Mix g g -g g of Removed for mains as Next Sample Starter Max Max Time ltjressu 'e '{empgrghrs Solubility Lbs Lbs. Lbs. Lbs. Lbs. Lbs Lbs. Lbs.

Lbs. Lbs. Lbs. Lbs Sol- Res- 801- Res- 501- Res- S01- Resvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to 15170.... Molal Ratio 1:14. 14.2 15.8 14.2 15.8 3. 3.1 3.4 0.75 11.1 12.4 2.5 150 1%: NS Ex. No. 114b...

Second Stage Third Stage Resin to EtO... Molal Ratio 1:10. 6.64 7.36 0 6.64 7.36 15.0 190 1% 8 Ex. N0. 1160.....

Fourth Stade Resin to 1110.... MolaLRatio 1:15. 4' 40 4.9 0 4.4 4.9 14.8 400 160 VS Ex. No. 1175...

Fifth Stage Resin to EtO.- Molal Ratio 1:20. 4. 1; 4.58 4. 62 4.1 4. 58 18.52 260 172 55 VS Ex. No. 118b S=Solub1e. NS=Not soluble. SS==Somewhat soluble. VS=Very soluble.

Phenol. for resin. Menthylphenol Aldehyde for resin: Formaldehyde Date, July 8-13, 1948 [Resin made in pilot plant size hatch, approximately 25 pounds; corresponding to- 69a of Patent 2,499,370 but this batch designated 119a.]

. Mix Which/is Mix Which Re- Starting Mix af figg of Removed for mains as Next Sample Starter Max. Max. nlareesure "{empgra- 1112 Solubility Lbs. Lbs. Lbs. Lbs; Lbs. Lbs. Lbs. Lbs.

Sol- Res- Sol- Res- S01- Res- Sol- Resvent in vent in vent in vent in First Stage Resin to Et0 MolaLRatiO. 1:1.. 13.65 16.35 0 13. 65 16. 35 3:0 9.55 11.45 2.1 4.1 4.9 0.9 60 1% NS Ex. No. 1195"-.-

Second Slade Third Stage Resin to 13150.... Mole] Ratiultlfl 5'. 48 6.58 5. 94 5.48 6.58 10.85 90 160 H S Ex. N0. 1215.....

Fourth Staae Resin to Et0..- Mala] Ratio 1:15. 4.1 4.9 0:9 4.1 4. 9' 13.15 180 171 1%2 VS Ex. N0. 1220"--- Fifth Stage Resin to EtO. Mom-Ratio 1120. 3.10 3. 72 0.68 3.10 3.72 13.43 320 VS Ex. No. 1235...

S=So1ub1e. NS=Not soluble. VS=Very soluble.

Date, July 14-15, 1948 Phenol for resin: Para-secondary. bntylphenol Aldehyde fo'reesinr Formaldehyde [Resin made in pilot pls'ni size batch, a proximately ponnds, berr'es oiidingie za'ei Patent. 2,499,370 but this batch designated 12411.]

Mix Which is Mix Which Re- Starting Mix Egg of Removed for mains as Next;

eac Sample Starter Max Pressu re Tem gera- 152? Solublmy Lbs. Lbs. Lb Lbs. Lbs. Lbs Lbs. Lbs. b5 Lbs. Lbs. Lbs tum Sol- Resg Sol- Res- Sol- Ress Sol- Resd vent in vent in vent in vent in First Stage Resin to EtO v M01211 Ratio 1: 14. 15. 0 14. 45 15. 55 4. 25 5. 97 6; 38 1. 75 8. 48 9. 17 2. 50 150 912 NS Ex. N0. 124b Second Stage Resinjso mo.--" v v 4 M0131 Ratio 1: 8. 48 9. 17 2. 50 8. 48 9. 17 16. 0 i 5. 83 6. 32 11. O5 2. 2. 85 4.95 188 95 SS Ex. N0. b v

Third Stage E Resin to EtO. I v V Molai Ratio 1:10 4. 82 5. 18 0 4. 82 5. 18 14. 25 400 183 12 S EX. N0. 1261) Fourth Stage Resin to EtO V Molal Ratio 1:15 3. 85 4.15 0 3.85 4.15 17. O 120 180 VS Ex. No. .1270

Fifth Stage Resin to Em.--" 7 i I r j Molal Ratio 1:20- 2. 65 2. 85 4.95 2. 65 2. 85 15. 45 80 170 $12 VS Ex. No. 128b S=Soluble. NS =N0t soluble. SS=SoiI1ewhat soluble. -VS=Very soluble.

Date August 12-13, 1948 1' Phenol fof resin: 'Menihyl" 1 Aldehyde for .re'sinfPropionaldehg de [Resin made on pilot plant size batch, approximately 25po1 1nds; corresponding t'o81a oi Petent'2, 499,370'but this batch designated 12911.1

- Mix Which is Mix Which Re- Starting Mix figg ggg of Removed for mains as Next Sample Starter Max fires-sum g & Tlfilsle, Solubility i i s. sq. m. are i s: i122: 35; si: 522: g g .122: 53g iii: gg vent in vent in vent in vent "in First Stage Resin to EtO V p Moial Ratio 1: 12.8 17. 12.8 17.2 2.75 4. 25 5. 7 0.95 8. 55 "11.50 1.80 110 16 Not soluble. Ex. N0. 1291) Second Stage Resin to Et0- Molal Ratio 1:5 8.55 11.50 1. 80 8.55 11.50 9.3 4. 78 6.42' 5.2 3.77 5.08 4.10 100: $3 Somewhat Ex. N0. l30b soluble.

Third Stage Resin to Eton--- v Molai Ratio 1:10.. 3. 77 5. 08 4. 10 3. 77 5. 08 13. 1 100 182 M2 Soluble. Ex. No. 131b Fourth Stage Resin to Et0 Molal Ratio 1:15- 5.2 7.0 5. 2 .7.0 .17.0 3. 10 4. 17 10. 13 2. 10 2'83 6.87 i 200 182 M 'Verysoiuble. Ex.No.132b

Fifth Stage Resin to EtO. Y "I i "r Moi-a1 Ratio 1:20- 2.10 2.83 (87 2. 10 ..2. 83 .9..12 T Li 90 56 .Very'olubl. EX. No. 13317....

Date, August 27-31, 1948 Aldehyde for resin: Furfural [Resin made on pilot p1ant size batch approximately 25pounds, corresponding to 42a of .Patent 2,499,370 but this batch designated as 134a.]

Mix Which is Mix Which Re- Starting Mix ig fi g of Removed for mains as Next Sample Starter Max. Max. Time Pressure Tem gerahrs Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. me

S01- Res- So1- Res- So1 Res- S Resvent in vent in vent in vent in First Stage Resin to Eton.-- Mo1alRat101:1- -11..2 18.0 11.2 18.0 3.5 2.75 4.4 0.85 8.45 13.6 2.65 120 135 k; N01; soluble. Ex. No.134b .1

Second Stage Resin to 121:0--- Mo1a1Ratio1:5. 8.45 13.6 2.65 8.45136 12.65 5.03 8.12 7.55 3.42 5.48 5.10 110 150 54 Somewhat Ex. No. 135bsoluble.

Third Stage Resin to EtO Molal Rati01:10 4.5 8.0 4.5 8.0 14.5 2.45 4.35 7.99 2.05 3.65 6.60 180 163 54 Soluble. Ex. No.136b

Fourth Stage Resin to EtO Mo1a1Batio1:15 3.42 5.48 5.10 3.42 5.48 15.10 180 188 Verysoluble. Ex. No.137b

Fifth Stage Resin to EtO- Mo1a1Rati01:20- 2.05 3.65 6.60 2.05 3.65 13.35 120 125 Verysolubie. Ex. No.138b

Date, Sept. 23-24,

Phenol for resin: Menthyl Aldehyde for resin: Furfural [Resin made on pilot size batch, approximately pounds, corresponding to 89a of Patent 2,499,370 but this batch designated as 139a] Mix Which is Mix Which Re- Starting Mix figg ggg of Removed for mains as Next Sample Starter Max. Max. Time Pressu e Temp erahrs Solubility i b s. abs. Lbs gb s. 115. Lbs lbls. 1112s. Lbs lbls. gbs. Lbs ture 0- es- 0- esos- 0- es vent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to Et0-- M0151 Retiol 10.25 17.75 10.25 17.75 2.5 2.65 4.60 0.65 7.6 13.15 1.85 90 150 16 Not soluble. Ex. No. 13912 Second Stage Resin to Et0 MolalRatiol 7.6 13.15 1.85 7.6 13.15 9.35 5.2 9.00 6.40 2.4 4.15 2.95 177 56 Somewhat Ex. No. 140b soluble.

Third Stage Resin to EtO Molal Ratio 1:10-- 4.22 6.98 4.22 5.98 10.0 165 $5 Soluble. Ex. No. 141b Fourth Stage Resin to EM)---" MolalRatiol 5 3.76 6.24 3.76 6.24 13.25 171 $5 Very'sdluble.

Ex. NO. 14217 Fifth Stage Resin to EtO Mo1a1Ratio1:20-- -2;4 4.15 2.95 2.4- 4.15 1 1.7 A 90 $5 Verysoluble. Ex. No. 1435------ 1 Date, October 7-8, 1948 [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 42a of Patent 2.499.370 with 206 parts by weight of cornn ercial para-octylphenol replacing 164 parts by Weight of para-tertiary amylphenol but this batch designated as 144a.]

' 'Phenol for-resin: Para-octyl. Aldehyde "1- resin: Furfural Mix Which is Mix Which Re- Starting Mix fi 23 of Removed for mains as Next Sample Starter Max. Max. Time Itljressure 'flemgegahrs Solubility Lbs Lbs Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

Lbs. Lbs. Lbs Lbs. Sol- Res- 801- Res- Sol- Res- Sol- Resvent in Eto vent in Eto vent in Eto vent in Eto First Stage Rosin to Et-O Molal Ratio 1:1 12. 1 18. 6 12.1 18.6 3. 0 1 5.38 8. 28 1. 34 I 6. 72 10.32 1. 66 80 150 M2 Insoluble. Ex. No. 144b-- r Second Stage I Slight tend- Resin to EtO ency to- Molal Ratio 1:5-- 9. 14. 25 9. 25 14. 25 11. 0 3. 73 5. 73 .4. 44 5.52 8. 52 6.56 100 177 542 ward be- Ex. No. lb coming so]- uble. Third Stage Resin to EtO. Molal Ratio 1:10 6. 72 10.32 1.66 6.72 10.32 14. 91 4. 97 7. 62 11.01 1. 2. 70 3.90 182 $4 Fairly solu- Ex. No. 1460".-- ble.

Fourth Stage Resin to Et0 -Molal Ratio 1:15 5.52 8. 52 6. 56 5. 52 8. 52 19. R1 100 176 )4; Readily sol- Ex. No. 14717..." uble.

Fifth Stage Resin to 1910.... Molal Ratio 1:20. 1.75 2. 70 3.90 1. 75 2. 70 8.4 '80 34 Quite solu- Ex. No. 1480--- 1 ble.

Date, October 11-13, 1948 Resin made on pilot plant size batch. approximately 25 pounds, corrcs paraphenylphcnul replacing 164 par Phenol for resin: Para-phenyl Aldehyde for resihf Furlfural pondi g to 42a of Patent 2.499.370 with parts by weight of commercial ts by welght of para-tertiary amylphenol but this batch designated as 14911.]

Mix Which is Mix Which Re- Starting Mix fig figg of Removed for mains as Next Sample tarter Max Max Time Pressure 'Iernp erahm Solubility Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Sol- Res- 801- Res- Sol- Res- Sol- Resvent in vent in vent in vent in First Stage Resin to EtO Molal Ratio 1 16.7 13.9 16.7 3.0 3.50 4.25 0.80 10.35 12.45 2.20 100 160 Insoluble.

Ex. No. 149b...-

Second Stage 1 Resin to Et0.... Slight tend- Molal Ratio l:5 10.35 12. 45 2.20 10.35 12. 45 12.20 5.15 6.19 6.06 5.20 a. 26 6.14 so 183 as ency Ex. N0. 1500"..-

bility. Third Stage Resin to EtO Molal Ratio 1:10. 8.90 10.7 8. 90 10.70 19.0 5.30 6. 38 11.32 3.60 4.32 7.68 90 193 A2 Fairly solu- Ex. No. 15117"..- ble.

Fourth Stage Res'1ntoEtO Molal Ratio 1:15- 5.20 6.26 6.14 5.20 6. 26 16. 100 171 Readily sol- Ex. No. 1520..... uble.

Fifth Stage Resin to Et0- i -Molal .Ratio 1:20 3.60 4. 32 7.68 3. 60 4.32 15.68 Samplesomewhat rubberyand gelat- 230 170- 2 Ex. No. 1530"..- I inous but fairly soluble r 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A MIXED HYDROPHILE ESTER IN WHICH THE ACYL RADICALS ARE THOSE OF A DETERGENT-FORMING MONOCARBOXY ACID HAVING AT LEAST 8 AND NOT OVER 32 CARBON ATOMS IN CONJUCTION WITH THE ACYL RADICAL OF A POLYCARBOXY ACID, AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER - INSOLUBLE PHENOL - ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 